EP1519239B1

EP1519239B1 - Organophotoreceptor with a charge transport material having at least two azine groups

Info

Publication number: EP1519239B1
Application number: EP04255821A
Authority: EP
Inventors: Nusrallah Jubran; Kam W. Law; Zbigniew Tokarski
Original assignee: Samsung Electronics Co Ltd
Current assignee: Samsung Electronics Co Ltd
Priority date: 2003-09-25
Filing date: 2004-09-24
Publication date: 2007-01-03
Anticipated expiration: 2024-09-24
Also published as: EP1519239A3; DE602004004026D1; CN1603963A; US20050069798A1; JP2005099808A; DE602004004026T2; KR100571929B1; US6955869B2; EP1519239A2; KR20050030522A

Description

This invention relates to organophotoreceptors suitable for use in electrophotography and, more specifically, to organophotoreceptors having a charge transport material with at least two azine groups.
In electrophotography, an organophotoreceptor in the form of a plate, disk, sheet, belt, drum or the like having an electrically insulating photoconductive element on an electrically conductive substrate is imaged by first uniformly electrostatically charging the surface of the photoconductive layer, and then exposing the charged surface to a pattern of light. The light exposure selectively dissipates the charge in the illuminated areas where light strikes the surface, thereby forming a pattern of charged and uncharged areas, referred to as a latent image. A liquid or solid toner is then provided in the vicinity of the latent image, and toner droplets or particles deposit in the vicinity of either the charged or uncharged areas to create a toned image on the surface of the photoconductive layer. The resulting toned image can be transferred to a suitable ultimate or intermediate receiving surface, such as paper, or the photoconductive layer can operate as an ultimate receptor for the image. The imaging process can be repeated many times to complete a single image, for example, by overlaying images of distinct color components or effect shadow images, such as overlaying images of distinct colors to form a full color final image, and/or to reproduce additional images.
Both single layer and multilayer photoconductive elements have been used. In single layer embodiments, a charge transport material and charge generating material are combined with a polymeric binder and then deposited on the electrically conductive substrate. In multilayer embodiments, the charge transport material and charge generating material are present in the element in separate layers, each of which can optionally be combined with a polymeric binder, deposited on the electrically conductive substrate. Two arrangements are possible for a two-layer photoconductive element. In one two-layer arrangement (the "dual layer" arrangement), the charge-generating layer is deposited on the electrically conductive substrate and the charge transport layer is deposited on top of the charge generating layer. In an alternate two-layer arrangement (the "inverted dual layer" arrangement), the order of the charge transport layer and charge generating layer is reversed.
In both the single and multilayer photoconductive elements, the purpose of the charge generating material is to generate charge carriers (i.e., holes and/or electrons) upon exposure to light. The purpose of the charge transport material is to accept at least one type of these charge carriers and transport them through the charge transport layer in order to facilitate discharge of a surface charge on the photoconductive element. The charge transport material can be a charge transport compound, an electron transport compound, or a combination of both. When a charge transport compound is used, the charge transport compound accepts the hole carriers and transports them through the layer with the charge transport compound. When an electron transport compound is used, the electron transport compound accepts the electron carriers and transports them through the layer with the electron transport compound.
Although many charge transport materials are known, there is the need for other charge transport materials to meet the various requirements of particular electrophotographic applications.
To produce high quality images, particularly after multiple cycles, it is desirable for the charge transport materials to form a homogeneous solution with the polymeric binder and remain approximately homogeneously distributed through the organophotoreceptor material during the cycling of the material. In addition, it is desirable to increase the amount of charge that the charge transport material can accept (indicated by a parameter known as the acceptance voltage or "V_acc"), and to reduce retention of that charge upon discharge (indicated by a parameter known as the discharge voltage or "V_dis").
An aim of the present invention is to provide organophotoreceptors, electrophotographic imaging apparatus, electrophotographic imaging processes, and charge transport materials generally featuring good and/or beneficial properties and preferably addressing at least some of the problems in the art.
There are many charge transport materials available for electrophotography, including, for example, pyrazoline derivatives, fluorene derivatives, oxadiazole derivatives, stilbene derivatives, hydrazone derivatives, carbazole hydrazone derivatives, triaryl amines, polyvinyl carbazole, polyvinyl pyrene, and polyacenaphthylene. However, at least some of the available charge transport materials may suffer some disadvantages and thus there is always the need for charge transport materials to meet the various requirements of electrophotography applications. This represents a further aim of the present invention.
A preferred aim of the present invention is to provide organophotoreceptors having good electrostatic properties.
Moreover, a further preferred aim of the present invention is to provide charge transport materials for organophotoreceptors featuring good mechanical and/or chemical properties, and/or a combination of good mechanical and electrostatic properties.
Suitably, a yet further aim of the present invention is to provide organophotoreceptors and electrophotographic imaging apparatus which can be used to provide high quality of images, even after repeated cycling, using electrophotographic apparatus employing the organophotoreceptors and electrophotographic imaging methods using the apparatus.
Other aims and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be apparent or obvious from the description, or may be apparent from, or learned by, practice of the invention.
According to the present invention there is provided an organophotoreceptor, an electrophotographic imaging apparatus, an electrophotographic imaging process, and a charge transport material, as set forth in the appended claims. Preferred features of the invention will be apparent from the dependent claims, and the description which follows.
Accordingly, this invention seeks to provide organophotoreceptors having good electrostatic properties such as high V_acc and low V_dis.
In a first aspect of the present invention there is provided an organophotoreceptor comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:

(a) a charge transport material having the formula
where n is an integer between 2 and 6, inclusive;
- R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;
- X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups can be optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;
- Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and
- Z is a fluorenylidene group; and
(b) a charge generating compound.

Preferably, Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
Preferably, Z is an alkoxycarbonyl-9-fluorenylidene group.
Preferably, Z is an alkoxycarbonyl-9-fluorenylidene group and the alkoxy group contains 1 to 20 carbon atoms.
Preferably, the photoconductive element of the organophotoreceptor further comprises a second charge transport material.
Preferably, the second charge transport material comprises a charge transport compound.
Preferably, the photoconductive element of the organophotoreceptor further comprises a binder.
The organophotoreceptor may be provided, for example, in the form of a plate, a flexible belt, a flexible disk, a sheet, a rigid drum, or a sheet around a rigid or compliant drum. In one embodiment, the organophotoreceptor includes: (a) a photoconductive element comprising the charge transport material, the charge generating compound, a second charge transport material, and a polymeric binder; and (b) the electrically conductive substrate.
In a second aspect of the present invention there is provided an electrophotographic imaging apparatus that comprises (a) a light imaging component; and (b) the organophotoreceptor as described herein oriented to receive light from the light imaging component. The apparatus can further comprise a liquid toner dispenser. The method of electrophotographic imaging with photoreceptors, containing the charge transport materials noted herein, is also described.
In a third aspect of the present invention there is provided an electrophotographic imaging process comprising (a) applying an electrical charge to a surface of the organophotoreceptor described herein; (b) imagewise exposing the surface of the organophotoreceptor to radiation to dissipate charge in selected areas and thereby form a pattern of at least relatively charged and uncharged areas on the surface; (c) contacting the surface with a toner, such as a liquid toner that includes a dispersion of colorant particles in an organic liquid, to create a toned image; and (d) transferring the toned image to a substrate.
In a fourth aspect of the present invention there is provided a charge transport material having the general formula (1) above, i.e. the formula
where n is an integer between 2 and 6, inclusive;

R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;
X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups can be optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;
Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and
Z is a fluorenylidene group.

The invention provides suitable charge transport materials for organophotoreceptors featuring a combination of good mechanical and electrostatic properties. The invention generally provides organophotoreceptors having good electrostatic properties such as high V_acc and low V_dis. These photoreceptors can be used successfully with liquid toners to produce high quality images. The high quality of the imaging system can be maintained after repeated cycling.
Other features and advantages of the invention will be apparent from the following description of the particular embodiments thereof, and from the claims.
Features described herein of the first, second, third and fourth aspects of the present invention, respectively, may be regarded as preferred features of other aspects of the present invention.
An organophotoreceptor as described herein has an electrically conductive substrate and a photoconductive element comprising a charge generating compound and a charge transport material having two azine groups linked through two carbazolyl groups. These charge transport materials generally have desirable properties as evidenced by their performance in organophotoreceptors for electrophotography. In particular, the charge transport materials of this invention generally have high charge carrier mobilities and good compatibility with various binder materials, and possess excellent electrophotographic properties. The organophotoreceptors according to this invention generally have a high photosensitivity, a low residual potential, and a high stability with respect to cycle testing, crystallization, and organophotoreceptor bending and stretching. The organophotoreceptors are particularly useful in laser printers and the like as well as fax machines, photocopiers, scanners and other electronic devices based on electrophotography. The use of these charge transport materials is described in more detail below in the context of laser printer use, although their application in other devices operating by electrophotography can be generalized from the discussion below.
As noted above, to produce high quality images, particularly after multiple cycles, it is desirable for the charge transport materials to form a homogeneous solution with the polymeric binder and remain approximately homogeneously distributed through the organophotoreceptor material during the cycling of the material. In addition, it is desirable to increase the amount of charge that the charge transport material can accept (indicated by a parameter known as the acceptance voltage or "V_acc"), and to reduce retention of that charge upon discharge (indicated by a parameter known as the discharge voltage or "V_dis").
The charge transport materials can be classified as charge transport compound or electron transport compound. There are many charge transport compounds and electron transport compounds known in the art for electrophotography. Non-limiting examples of charge transport compounds include, for example, pyrazoline derivatives, fluorene derivatives, oxadiazole derivatives, stilbene derivatives, hydrazone derivatives, carbazole hydrazone derivatives, triaryl amines, polyvinyl carbazole, polyvinyl pyrene, polyacenaphthylene, or multi-hydrazone compounds comprising at least two hydrazone groups and at least two groups selected from the group consisting of p-(N,N-disubstituted) arylamine such as triphenylamine and heterocycles such as carbazole, julolidine, phenothiazine, phenazine, phenoxazine, phenoxathiin, thiazole, oxazole, isoxazole, dibenzo(1,4)dioxine, thianthrene, imidazole, benzothiazole, benzotriazole, benzoxazole, benzimidazole, quinoline, isoquinoline, quinoxaline, indole, indazole, pyrrole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazole, oxadiazole, tetrazole, thiadiazole, benzisoxazole, benzisothiazole, dibenzofuran, dibenzothiophene, thiophene, thianaphthene, quinazoline, or cinnoline.
Non-limiting examples of electron transport compounds include, for example, bromoaniline, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-indeno4H-indeno[1,2-b]thiophene-4-one, and 1,3,7-trinitrodibenzo thiophene-5,5-dioxide, (2,3-diphenyl-1-indenylidene)malononitrile, 4H-thiopyran-1,1-dioxide and its derivatives such as 4-dicyanomethylene-2,6-diphenyl-4H-thiopyran-1,1 -dioxide, 4-dicyanomethylene-2,6-di-m-tolyl-4H-thiopyran-1,1-dioxide, and unsymmetrically substituted 2,6-diaryl-4H-thiopyran-1,1-dioxide such as 4H-1,1-dioxo-2-(p-isopropylphenyl)-6-phenyl-4-(dicyanomethylidene)thiopyran and 4H-1,1-dioxo-2-(p-isopropylphenyl)-6-(2-thienyl)-4-(dicyanomethylidene)thiopyran, derivatives of phospha-2,5-cyclohexadiene, alkoxycarbonyl-9-fluorenylidene)malononitrile derivatives such as (4-n-butoxycarbonyl-9-fluorenylidene)malononitrile, (4-phenethoxycarbonyl-9-fluorenylidene)malononitrile, (4-carbitoxy-9-fluorenylidene)malononitrile, and diethyl(4-n-butoxycarbonyl-2,7-dinitro-9-fluorenylidene)-malonate, anthraquinodimethane derivatives such as 11,11,12,12-tetracyano-2-alkylanthraquinodimethane and 11,11-dicyano-12,12-bis(ethoxycarbonyl)anthraquinodimethane, anthrone derivatives such as 1-chloro-10-[bis(ethoxycarbonyl)methylene]anthrone, 1,8-dichloro-10-[bis(ethoxycarbonyl) methylene]anthrone, 1,8-dihydroxy-10-[bis(ethoxycarbonyl)methylene]anthrone, and 1-cyano-10-[bis(ethoxycarbonyl)methylene)anthrone, 7-nitro-2-aza-9-fluroenylidene-malononitrile, diphenoquinone derivatives, benzoquinone derivatives, naphtoquinone derivatives, quinine derivatives, tetracyanoethylenecyanoethylene, 2,4,8-trinitro thioxantone, dinitrobenzene derivatives, dinitroanthracene derivatives, dinitroacridine derivatives, nitroanthraquinone derivatives, dinitroanthraquinone derivatives, succinic anhydride, maleic anhydride, dibromo maleic anhydride, pyrene derivatives, carbazole derivatives, hydrazone derivatives, N,N-dialkylaniline derivatives, diphenylamine derivatives, triphenylamine derivatives, triphenylmethane derivatives, tetracyano quinoedimethane, 2,4,5,7-tetranitro-9-fluorenone, 2,4,7-trinitro-9-dicyanomethylene fluorenone, 2,4,5,7-tetranitroxanthone derivatives, and 2,4,8-trinitrothioxanthone derivatives. In some embodiments of interest, the electron transport compound comprises an (alkoxycarbonyl-9-fluorenylidene)malononitrile derivative, such as (4-n-butoxycarbonyl-9-fluorenylidene)malononitrile.
Although there are many charge, transport materials available, there remains, as noted above, the need for other charge transport materials to meet the various requirements of particular electrophotography applications.
In electrophotography applications, a charge-generating compound within an organophotoreceptor absorbs light to form electron-hole pairs. These electrons and holes can be transported over an appropriate time frame under a large electric field to discharge locally a surface charge that is generating the field. The discharge of the field at a particular location results in a surface charge pattern that essentially matches the pattern drawn with the light. This charge pattern then can be used to guide toner deposition. The charge transport materials described herein are generally especially effective at transporting charge, and in particular electrons from the electron-hole pairs formed by the charge generating compound. In some embodiments, a specific electron transport compound or charge transport compound can also be used along with the charge transport material of this invention.
The layer or layers of materials containing the charge generating compound and the charge transport materials are within an organophotoreceptor. To print a two dimensional image using the organophotoreceptor, the organophotoreceptor has a two dimensional surface for forming at least a portion of the image. The imaging process then continues by cycling the organophotoreceptor to complete the formation of the entire image and/or for the processing of subsequent images.
The organophotoreceptor may be provided in the form of a plate, a flexible belt, a disk, a rigid drum, a sheet around a rigid or compliant drum, or the like. The charge transport material can be in the same layer as the charge generating compound and/or in a different layer from the charge generating compound. Additional layers can be used also, as described further below.
In some embodiments, the organophotoreceptor material comprises, for example: (a) a charge transport layer comprising the charge transport material and a polymeric binder; (b) a charge generating layer comprising the charge generating compound and a polymeric binder; and (c) the electrically conductive substrate. The charge transport layer may be intermediate between the charge generating layer and the electrically conductive substrate. Alternatively, the charge generating layer may be intermediate between the charge transport layer and the electrically conductive substrate. In further embodiments, the organophotoreceptor material has a single layer with both a charge transport material and a charge generating compound within a polymeric binder.
The organophotoreceptors can be incorporated into an electrophotographic imaging apparatus, such as laser printers. In these devices, an image is formed from physical embodiments and converted to a light image that is scanned onto the organophotoreceptor to form a surface latent image. The surface latent image can be used to attract toner onto the surface of the organophotoreceptor, in which the toner image is the same or the negative of the light image projected onto the organophotoreceptor. The toner can be a liquid toner or a dry toner. The toner is subsequently transferred, from the surface of the organophotoreceptor, to a receiving surface, such as a sheet of paper. After the transfer of the toner, the entire surface is discharged, and the material is ready to cycle again. The imaging apparatus can further comprise, for example, a plurality of support rollers for transporting a paper receiving medium and/or for movement of the photoreceptor, a light imaging component with suitable optics to form the light image, a light source, such as a laser, a toner source and delivery system and an appropriate control system.
An electrophotographic imaging process generally can comprise (a) applying an electrical charge to a surface of the organophotoreceptor described herein; (b) imagewise exposing the surface of the organophotoreceptor to radiation to dissipate charge in selected areas and thereby form a pattern of charged and uncharged areas on the surface; (c) exposing the surface with a toner, such as a liquid toner that includes a dispersion of colorant particles in an organic liquid to create a toner image, to attract toner to the charged or discharged regions of the organophotoreceptor; and (d) transferring the toner image to a substrate.
As described herein, in an aspect of the present invention, an organophotoreceptor comprises a charge transport material having the formula
where n is an integer between 2 and 6, inclusive;

R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;
X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups is optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;
Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and
Z is a fluorenylidene group.

In some embodiments, n is 2.
In some embodiments,Y is a bond.
In some embodiments, X is a -(CH₂)_m- group where m is an integer between 1 and 20.
Preferably, Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
Preferably, Z is an alkoxycarbonyl-9-fluorenylidene group.
Preferably, Z is an alkoxycarbonyl-9-fluorenylidene group and the alkoxy group contains 1 to 20 carbon atoms.
In some embodiments, Z is an alkoxycarbonyl-9-fluorenylidene group wherein the alkoxy group contains 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, notably 2 or 4 carbon atoms.
In some embodiments, Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 10, notably 4, 5 or 6, and one or more of the methylene groups is optionally replaced by O or C=O.
In some embodiments, R₁ and R₂ are both H.
Preferably, the photoconductive element of the organophotoreceptor further comprises a second charge transport material.
Preferably, the second charge transport material comprises a charge transport compound.
Preferably, the photoconductive element of the organophotoreceptor further comprises a binder.
Substitution is liberally allowed on the chemical groups to affect various physical effects on the properties of the compounds, such as mobility, sensitivity, solubility, stability, and the like, as is known generally in the art. In the description of chemical substituents, there are certain practices common to the art that are reflected in the use of language. The term group indicates that the generically recited chemical entity (e.g., alkyl group, phenyl group, fluorenylidene group, etc.) may have any substituent thereon which is consistent with the bond structure of that group. For example, where the term 'alkyl group' is used, that term would not only include unsubstituted liner, branched and cyclic alkyls, such as methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, dodecyl and the like, but also substituents such as hydroxyethyl, cyanobutyl, 1,2,3-trichloropropane, and the like. However, as is consistent with such nomenclature, no substitution would be included within the term that would alter the fundamental bond structure of the underlying group. For example, where a phenyl group is recited, substitution such as 1-hydroxyphenyl, 2,4-fluorophenyl, orthocyanophenyl, 1,3,5-trimethoxyphenyl and the like would be acceptable within the terminology, while substitution of 1,1,2,2,3,3-hexamethylphenyl would not be acceptable as that substitution would require the ring bond structure of the phenyl group to be altered to a non-aromatic form because of the substitution. Similarly, when referring to fluorenylidene group, the compound or substituent cited will include any substitution that does not substantively alter the chemical nature of the fluorenylidene ring in the formula. Where the term moiety is used, such as alkyl moiety or phenyl moiety, the moiety terminology indicates that the chemical material is not substituted. Where the term alkyl moiety is used, that term represents only an unsubstituted alkyl hydrocarbon group, whether branched, straight chain, or cyclic.
In general, and except where stated otherwise herein, the following apply. Preferred alkyl groups are C_1-16 alkyl, especially C_1-12 alkyl, more especially C_1-8 alkyl, even more especially C_1-4 alkyl, suitably substituted or unsubstituted, suitably linear, branched or cyclic. Preferred halogen atoms are bromine, fluorine and chlorine.

Organophotoreceptors

The organophotoreceptor may be, for example, in the form of a plate, a sheet, a flexible belt, a disk, a rigid drum, or a sheet around a rigid or compliant drum, with flexible belts and rigid drums generally being used in commercial embodiments. The organophotoreceptor may comprise, for example, an electrically conductive substrate and on the electrically conductive substrate a photoconductive element in the form of one or more layers. The photoconductive element can comprise both a charge transport material and a charge generating compound in a polymeric binder, which may or may not be in the same layer, as well as a second charge transport material such as a charge transport compound or an electron transport compound in some embodiments. For example, the charge transport material and the charge generating compound can be in a single layer. In other embodiments, however, the photoconductive element comprises a bilayer construction featuring a charge generating layer and a separate charge transport layer. The charge generating layer may be located intermediate between the electrically conductive substrate and the charge transport layer. Alternatively, the photoconductive element may have a structure in which the charge transport layer is intermediate between the electrically conductive substrate and the charge generating layer.
The electrically conductive substrate may be flexible, for example in the form of a flexible web or a belt, or inflexible, for example in the form of a drum. A drum can have a hollow cylindrical structure that provides for attachment of the drum to a drive that rotates the drum during the imaging process. Typically, a flexible electrically conductive substrate comprises an electrically insulating substrate and a thin layer of electrically conductive material onto which the photoconductive material is applied.
The electrically insulating substrate may be paper or a film forming polymer such as polyester (e.g., polyethylene terephthalate or polyethylene naphthalate), polyimide, polysulfone, polypropylene, nylon, polyester, polycarbonate, polyvinyl resin, polyvinyl fluoride, polystyrene and the like. Specific examples of polymers for supporting substrates included, for example, polyethersulfone (Stabar^™ S-100, available from ICI), polyvinyl fluoride (Tedlar^®, available from E.I. DuPont de Nemours & Company), polybisphenol-A polycarbonate (Makrofol^™, available from Mobay Chemical Company) and amorphous polyethylene terephthalate (Melinar^™, available from ICI Americas, Inc.). The electrically conductive materials may be graphite, dispersed carbon black, iodide, conductive polymers such as polypyroles and Calgon^® conductive polymer 261 (commercially available from Calgon Corporation, Inc., Pittsburgh, Pa.), metals such as aluminum, titanium, chromium, brass, gold, copper, palladium, nickel, or stainless steel, or metal oxide such as tin oxide or indium oxide. In embodiments of particular interest, the electrically conductive material is aluminum. Generally, the photoconductor substrate has a thickness adequate to provide the required mechanical stability. For example, flexible web substrates generally have a thickness from about 0.01 to about 1 mm, while drum substrates generally have a thickness of from about 0.5 mm to about 2 mm.
The charge generating compound is a material that is capable of absorbing light to generate charge carriers, such as a dye or pigment. Non-limiting examples of suitable charge generating compounds include, for example, metal-free phthalocyanines (e.g., ELA 8034 metal-free phthalocyanine available from H.W. Sands, Inc. or Sanyo Color Works, Ltd., CGM-X01), metal phthalocyanines such as titanium phthalocyanine, copper phthalocyanine, oxytitanium phthalocyanine (also referred to as titanyl oxyphthalocyanine, and including any crystalline phase or mixtures of crystalline phases that can act as a charge generating compound), hydroxygallium phthalocyanine, squarylium dyes and pigments, hydroxy-substituted squarylium pigments, perylimides, polynuclear quinones available from Allied Chemical Corporation under the tradename Indofast^® Double Scarlet, Indofast^® Violet Lake B, Indofast^® Brilliant Scarlet and Indofast^® Orange, quinacridones available from DuPont under the tradename Monastral^™ Red, Monastral^™ Violet and Monastral^™ Red Y, naphthalene 1,4,5,8-tetracarboxylic acid derived pigments including the perinones, tetrabenzoporphyrins and tetranaphthaloporphyrins, indigo- and thioindigo dyes, benzothioxanthene-derivatives, perylene 3,4,9,10-tetracarboxylic acid derived pigments, polyazo-pigments including bisazo-, trisazo- and tetrakisazo-pigments, polymethine dyes, dyes containing quinazoline groups, tertiary amines, amorphous selenium, selenium alloys such as selenium-tellurium, selenium-tellurium-arsenic and selenium-arsenic, cadmium sulphoselenide, cadmium selenide, cadmium sulphide, and mixtures thereof. For some embodiments, the charge generating compound comprises oxytitanium phthalocyanine (e.g., any phase thereof), hydroxygallium phthalocyanine or a combination thereof.
The photoconductive layer of this invention may optionally contain a second charge transport material, which may be a charge transport compound, an electron transport compound, or a combination of both. Generally, any charge transport compound or electron transport compound known in the art can be used as the second charge transport material.
An electron transport compound and a UV light stabilizer can have a synergistic relationship for providing desired electron flow within the photoconductor. The presence of the UV light stabilizers alters the electron transport properties of the electron transport compounds to improve the electron transporting properties of the composite. UV light stabilizers can be ultraviolet light absorbers or ultraviolet light inhibitors that trap free radicals.
UV light absorbers can absorb ultraviolet radiation and dissipate it as heat. UV light inhibitors are thought to trap free radicals generated by the ultraviolet light and after trapping of the free radicals, subsequently to regenerate active stabilizer moieties with energy dissipation. In view of the synergistic relationship of the UV stabilizers with electron transport compounds, the particular advantages of the UV stabilizers may not be their UV stabilizing abilities, although the UV stabilizing ability may be further advantageous in reducing degradation of the organophotoreceptor over time. The improved synergistic performance of organophotoreceptors with layers comprising both an electron transport compound and a UV stabilizer are described further in copending U.S. Patent Application Serial Number 10/425,333 filed on April 28, 2003 to Zhu, entitled "Organophotoreceptor With A Light Stabilizer," published as US 2003/0228534 A1.
Non-limiting examples of suitable light stabilizer include, for example, hindered trialkylamines such as Tinuvin 144 and Tinuvin 292 (from Ciba Specialty Chemicals, Terrytown, NY), hindered alkoxydialkylamines such as Tinuvin 123 (from Ciba Specialty Chemicals), benzotriazoles such as Tinuvan 328, Tinuvin 900 and Tinuvin 928 (from Ciba Specialty Chemicals), benzophenones such as Sanduvor 3041 (from Clariant Corp., Charlotte, N.C.), nickel compounds such as Arbestab (from Robinson Brothers Ltd, West Midlands, Great Britain), salicylates, cyanocinnamates, benzylidene malonates, benzoates, oxanilides such as Sanduvor VSU (from Clariant Corp., Charlotte, N.C.), triazines such as Cyagard UV-1164 (from Cytec Industries Inc., N.J.), polymeric sterically hindered amines such as Luchem (from Atochem North America, Buffalo, NY). In some embodiments, the light stabilizer is selected from the group consisting of hindered trialkylamines having the following formula:
where R₁, R₂, R₃, R₄, R₆, R₇, R₈, R₁₀, R₁₁, R₁₂, R₁₃, R₁₅ and R₁₆ are, independently, hydrogen, alkyl group, or ester, or ether group; and R₅, R₉, and R₁₄ are, independently, alkyl group; and X is a linking group selected from the group consisting of -O-CO-(CH₂)_m-CO-O- where m is between 2 to 20.
The binder generally is capable of dispersing or dissolving the charge transport material (in the case of the charge transport layer or a single layer construction), the charge generating compound (in the case of the charge generating layer or a single layer construction) and/or an electron transport compound for appropriate embodiments. Examples of suitable binders for both the charge generating layer and charge transport layer generally include, for example, polystyrene-co-butadiene, polystyrene-co- acrylonitrile, modified acrylic polymers, polyvinyl acetate, styrene-alkyd resins, soya-alkyl resins, polyvinylchloride, polyvinylidene chloride, polyacrylonitrile, polycarbonates, polyacrylic acid, polyacrylates, polymethacrylates, styrene polymers, polyvinyl butyral, alkyd resins, polyamides, polyurethanes, polyesters, polysulfones, polyethers, polyketones, phenoxy resins, epoxy resins, silicone resins, polysiloxanes, poly(hydroxyether) resins, polyhydroxystyrene resins, novolak, poly(phenylglycidyl ether)-co-dicyclopentadiene, copolymers of monomers used in the above-mentioned polymers, and combinations thereof. Suitable binders include, for example, polyvinyl butyral, such as BX-1 and BX-5 from Sekisui Chemical Co. Ltd., Japan.
Suitable optional additives for any one or more of the layers include, for example, antioxidants, coupling agents, dispersing agents, curing agents, surfactants, and combinations thereof.
The photoconductive element overall typically has a thickness from about 10 to about 45 microns. In the dual layer embodiments having a separate charge generating layer and a separate charge transport layer, the charge generation layer generally has a thickness form about 0.5 to about 2 microns, and the charge transport layer has a thickness from about 5 to about 35 microns. In embodiments in which the charge transport material and the charge generating compound are in the same layer, the layer with the charge generating compound and the charge transport composition generally has a thickness from about 7 to about 30 microns. In embodiments with a distinct electron transport layer, the electron transport layer has an average thickness from about 0.5 microns to about 10 microns and in further embodiments from about 1 micron to about 3 microns. In general, an electron transport overcoat layer can increase mechanical abrasion resistance, increases resistance to carrier liquid and atmospheric moisture, and decreases degradation of the photoreceptor by corona gases. A person of ordinary skill in the art will recognize that additional ranges of thickness within the explicit ranges above are contemplated and are within the present disclosure.
Generally, for the organophotoreceptors described herein, the charge generation compound is in an amount from about 0.5 to about 25 weight percent in further embodiments in an amount from about 1 to about 15 weight percent and in other embodiments in an amount from about 2 to about 10 weight percent, based on the weight of the photoconductive layer. Suitably, the charge transport material is in an amount from about 10 to about 80 weight percent, based on the weight of the photoconductive layer, in further embodiments in an amount from about 35 to about 60 weight percent, and in other embodiments from about 45 to about 55 weight percent, based on the weight of the photoconductive layer. The optional second charge transport material, when present, can be in an amount of at least about 2 weight percent, in other embodiments from about 2.5 to about 25 weight percent, based on the weight of the photoconductive layer, and in further embodiments in an amount from about 4 to about 20 weight percent, based on the weight of the photoconductive layer. Suitably, the binder is in an amount from about 15 to about 80 weight percent, based on the weight of the photoconductive layer, and in further embodiments in an amount from about 20 to about 75 weight percent, based on the weight of the photoconductive layer. A person of ordinary skill in the art will recognize that additional ranges within the explicit ranges of compositions are contemplated and are within the present disclosure.
For the dual layer embodiments with a separate charge generating layer and a charge transport layer, the charge generation layer generally comprises a binder in an amount from about 10 to about 90 weight percent, in further embodiments from about 15 to about 80 weight percent and in some embodiments in an amount of from about 20 to about 75 weight percent, based on the weight of the charge generation layer. The optional charge transport material in the charge generating layer, if present, generally can be in an amount of at least about 2.5 weight percent, in further embodiments from about 4 to about 30 weight percent and in other embodiments in an amount from about 10 to about 25 weight percent, based on the weight of the charge generating layer. The charge transport layer generally comprises a binder in an amount from about 20 weight percent to about 70 weight percent and in further embodiments in an amount from about 30 weight percent to about 50 weight percent. A person of ordinary skill in the art will recognize that additional ranges of binder concentrations for the dual layer embodiments within the explicit ranges above are contemplated and are within the present disclosure.
For the embodiments with a single layer having a charge generating compound and a charge transport material, the photoconductive layer generally comprises a binder, a charge transport material, and a charge generation compound. The charge generation compound can be in an amount from about 0.05 to about 25 weight percent and in further embodiment in an amount from about 2 to about 15 weight percent, based on the weight of the photoconductive layer. The charge transport material can be in an amount from about 10 to about 80 weight percent, in other embodiments from about 25 to about 65 weight percent, in additional embodiments from about 30 to about 60 weight percent and in further embodiments in an amount from about 35 to about 55 weight percent, based on the weight of the photoconductive layer, with the remainder of the photoconductive layer comprising the binder, and optionally additives, such as any conventional additives. A single layer with a charge transport composition and a charge generating compound generally comprises a binder in an amount from about 10 weight percent to about 75 weight percent, in other embodiments from about 20 weight percent to about 60 weight percent, and in further embodiments from about 25 weight percent to about 50 weight percent. Optionally, the layer with the charge generating compound and the charge transport material may comprise a second charge transport material. The optional second charge transport material, if present, generally can be in an amount of at least about 2.5 weight percent, in further embodiments from about 4 to about 30 weight percent and in other embodiments in an amount from about 10 to about 25 weight percent, based on the weight of the photoconductive layer. A person of ordinary skill in the art will recognize that additional composition ranges within the explicit compositions ranges for the layers above are contemplated and are within the present disclosure.
In general, any layer with an electron transport layer can advantageously further include a UV light stabilizer. In particular, the electron transport layer generally can comprise an electron transport compound, a binder, and an optional UV light stabilizer. An overcoat layer comprising an electron transport compound is described further in copending U.S. Patent Application Serial No. 10/396,536 to Zhu et al. entitled, "Organophotoreceptor With An Electron Transport Layer," published as US 2003/0194626 A1. For example, an electron transport compound as described above may be used in the release layer of the photoconductors described herein. Suitably, the electron transport compound in an electron transport layer can be in an amount from about 10 to about 50 weight percent, and in other embodiments in an amount from about 20 to about 40 weight percent, based on the weight of the electron transport layer. A person of ordinary skill in the art will recognize that additional ranges of compositions within the explicit ranges are contemplated and are within the present disclosure.
The UV light stabilizer, if present, in any one or more appropriate layers of the photoconductor generally is suitably in an amount from about 0.5 to about 25 weight percent and in some embodiments in an amount from about 1 to about 10 weight percent, based on the weight of the particular layer. A person of ordinary skill in the art will recognize that additional ranges of compositions within the explicit ranges are contemplated and are within the present disclosure.
For example, the photoconductive layer may be formed by dispersing or dissolving the components, such as one or more of a charge generating compound, the charge transport material of this invention, a second charge transport material such as a charge transport compound or an electron transport compound, a UV light stabilizer, and a polymeric binder in organic solvent, coating the dispersion and/or solution on the respective underlying layer and drying the coating. In particular, the components can be dispersed by high shear homogenization, ball-milling, attritor milling, high energy bead (sand) milling or other size reduction processes or mixing means known in the art for effecting particle size reduction in forming a dispersion.
The photoreceptor may optionally have one or more additional layers as well. An additional layer can be, for example, a sub-layer or an overcoat layer, such as a barrier layer, a release layer, a protective layer, or an adhesive layer. A release layer or a protective layer may form the uppermost layer of the photoconductor element. A barrier layer may be sandwiched between the release layer and the photoconductive element or used to overcoat the photoconductive element. The barrier layer provides protection from abrasion to the underlayers. An adhesive layer locates and improves the adhesion between a photoconductive element, a barrier layer and a release layer, or any combination thereof. A sub-layer is a charge blocking layer and locates between the electrically conductive substrate and the photoconductive element. The sub-layer may also improve the adhesion between the electrically conductive substrate and the photoconductive element.
Suitable barrier layers include, for example, coatings such as crosslinkable siloxanol-colloidal silica coating and hydroxylated silsesquioxane-colloidal silica coating, and organic binders such as polyvinyl alcohol, methyl vinyl ether/maleic anhydride copolymer, casein, polyvinyl pyrrolidone, polyacrylic acid, gelatin, starch, polyurethanes, polyimides, polyesters, polyamides, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polycarbonates, polyvinyl butyral, polyvinyl acetoacetal, polyvinyl formal, polyacrylonitrile, polymethyl methacrylate, polyacrylates, polyvinyl carbazoles, copolymers of monomers used in the above-mentioned polymers, vinyl chloride/vinyl acetate/vinyl alcohol terpolymers, vinyl chloride/vinyl acetate/maleic acid terpolymers, ethylene/vinyl acetate copolymers, vinyl chloride/vinylidene chloride copolymers, cellulose polymers, and mixtures thereof. The above barrier layer polymers optionally may contain small inorganic particles such as fumed silica, silica, titania, alumina, zirconia, or a combination thereof. Barrier layers are described further in U.S. Patent 6,001,522 to Woo et al., entitled "Barrier Layer For Photoconductor Elements Comprising An Organic Polymer And Silica,". The release layer topcoat may comprise any release layer composition known in the art. In some embodiments, the release layer is a fluorinated polymer, siloxane polymer, fluorosilicone polymer, silane, polyethylene, polypropylene, polyacrylate, or a combination thereof. The release layers can comprise crosslinked polymers.
The release layer may comprise, for example, any release layer composition known in the art. In some embodiments, the release layer comprises a fluorinated polymer, siloxane polymer, fluorosilicone polymer, polysilane, polyethylene, polypropylene, polyacrylate, poly(methyl methacrylate-co-methacrylic acid), urethane resins, urethane-epoxy resins, acrylated-urethane resins, urethane-acrylic resins, or a combination thereof. In further embodiments, the release layers comprise crosslinked polymers.
The protective layer can protect the organophotoreceptor from chemical and mechanical degradation. The protective layer may comprise any protective layer composition known in the art. In some embodiments, the protective layer is a fluorinated polymer, siloxane polymer, fluorosilicone polymer, polysilane, polyethylene, polypropylene, polyacrylate, poly(methyl methacrylate-co-methacrylic acid), urethane resins, urethane-epoxy resins, acrylated-urethane resins, urethane-acrylic resins, or a combination thereof. In some embodiments of particular interest, the release layers are crosslinked polymers.
An overcoat layer may comprise an electron transport compound as described further in copending U.S. Patent Application Serial No. 10/396,536, filed on March 25, 2003 to Zhu et al. entitled, "Organoreceptor With An Electron Transport Layer," published as US 2003/0194626 A1. For example, an electron transport compound, as described above, may be used in the release layer of this invention. Suitably, the electron transport compound in the overcoat layer can be in an amount from about 2 to about 50 weight percent, and in other embodiments in an amount from about 10 to about 40 weight percent, based on the weight of the release layer. A person of ordinary skill in the art will recognize that additional ranges of composition within the explicit ranges are contemplated and are within the present disclosure.
Generally, adhesive layers comprise a film forming polymer, such as polyester, polyvinylbutyral, polyvinylpyrolidone, polyurethane, polymethyl methacrylate, poly(hydroxy amino ether) and the like. Barrier and adhesive layers are described further in U.S. Patent 6,180,305 to Ackley et al., entitled "Organic Photoreceptors for Liquid Electrophotography,".
Sub-layers can comprise, for example, polyvinylbutyral, organosilanes, hydrolyzable silanes, epoxy resins, polyesters, polyamides, polyurethanes, silicones, and the like. In some embodiments, the sub-layer has a dry thickness between about 20 Angstroms and about 2,000 Angstroms. Sublayers containing metal oxide conductive particles can be between about 1 and about 25 microns thick. A person of ordinary skill in the art will recognize that additional ranges of compositions and thickness within the explicit ranges are contemplated and are within the present disclosure.
The charge transport materials as described herein, and photoreceptors including these compounds, are suitable for use in an imaging process with either dry or liquid toner development. For example, any dry toners and liquid toners known in the art may be used in the process and the apparatus of this invention. Liquid toner development can be desirable because it offers the advantages of providing higher resolution images and requiring lower energy for image fixing compared to dry toners. Examples of suitable liquid toners are known in the art. Liquid toners generally comprise toner particles dispersed in a carrier liquid. The toner particles can comprise a colorant/pigment, a resin binder, and/or a charge director. In some embodiments of liquid toner, a resin to pigment ratio can be from 1:1 to 10:1, and in other embodiments, from 4:1 to 8:1. Liquid toners are described further in Published U.S. Patent Applications 2002/0128349, entitled "Liquid Inks Comprising A Stable Organosol," 2002/0086916, entitled "Liquid Inks Comprising Treated Colorant Particles," and 2002/0197552, entitled "Phase Change Developer For Liquid Electrophotography,".

Charge Transport Material

As described herein, an organophotoreceptor comprises a charge transport material having the formula
where n is an integer between 2 and 6, inclusive;

In some embodiments, n is 2.
In some embodiments,Y is a bond.
In some embodiments, X is a -(CH₂)_m- group where m is an integer between 1 and 20.
Preferably, Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
Preferably, Z is an alkoxycarbonyl-9-fluorenylidene group.
Preferably, Z is an alkoxycarbonyl-9-fluorenylidene group and the alkoxy group contains 1 to 20 carbon atoms.
In some embodiments, Z is an alkoxycarbonyl-9-fluorenylidene group wherein the alkoxy group contains 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, notably 2 or 4 carbon atoms.
In some embodiments, Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 10, notably 4, 5 or 6, and one or more of the methylene groups is optionally replaced by O or C=O.
In some embodiments, R₁ and R₂ are both H.
Specific, non-limiting examples of suitable charge transport materials within the general Formula (1) of the present invention have the following structures (2) - (6):

Synthesis Of Charge Transport Materials

The synthesis of the charge transport materials of this invention can be prepared by the reaction of a bis(3-formyl-9-carbazolyl)alkane or its derivative and the hydrazone of a fluorenone-carboxylic acid alkyl ester. The synthesis of bis(3-formyl-9-carbazoyl)alkanes is disclosed in U.S. Patent 6,066,426. The hydrazone of fluorenone-carboxylic acid alkyl ester can be prepared by the reaction of fluorenone-carboxylic acid alkyl ester and hydrazine. Fluorenone-carboxylic acid alkyl ester can be prepared by the esterification reaction of an alcohol with fluorenone-carboxylic acid (available from Aldrich, Milwaukee, WI).
The invention will now be described further by way of the following illustrative examples. These examples are to be viewed as being illustrative of specific materials falling within the broader disclosure presented above.

EXAMPLES

Example 1 - Synthesis And Characterization Charge Transport Materials

This example described the synthesis and characterization of Compounds 2-6 in which the numbers refer to formula numbers above. The characterization involves both chemical characterization and the electronic characterization of materials formed with the compound.

Preparation of (4-n-Butoxycarbonyl-9-fluorenylidene)malononitrile

A 70 g (0.312 mole) quantity of fluorenone-4-carboxylic acid (commercially available from Aldrich, Milwaukee, WI), 480 g (6.5 mole) of n-butanol (commercially obtained from Fisher Scientific Company Inc., Hanover Park, IL), 1000 ml of toluene and 4 ml of concentrated sulfuric acid were added to a 2-liter round bottom flask equipped with a mechanical stirrer and a reflux condenser with a Dean Stark apparatus. The solution was refluxed for 5 hours with aggressive agitation and refluxing, during which time about 6 g of water were collected in the Dean Stark apparatus. The flask was cooled to room temperature. The solvents were evaporated and the residue was added to 4-liter of 3% sodium bicarbonate aqueous solution with agitation. The solid was filtered off, washed with water until the pH of the water was neutral, and dried in the hood overnight. The product was n-butyl fluorenone-4-carboxylate ester (70 g, 80% yield). A ¹H-NMR spectrum of n-butyl fluorenone-4-carboxylate ester was obtained in CDCl₃ with a 300 MHz NMR from Bruker Instrument. The peaks (in ppm) were found at δ = 0.87 -1.09 (t, 3H); δ = 1.42 - 1.70 (m, 2H); δ = 1.75 - 1.88 (q, 2H); δ = 4.26 - 4.64 (t, 2H); δ = 7.29 -7.45 (m, 2H); δ = 7.46 -7.58 (m, 1H); δ = 7.60 - 7.68 (dd, 1H); δ = 7.75 - 7.82 (dd, 1H); δ = 7.90 -8.00 (dd, 1H); δ = 8.25 - 8.35 (dd, 1H).
A 70 g (0.25 mole) quantity of n-butyl fluorenone-4-carboxylate ester, 750 ml of absolute methanol, 37 g (0.55 mole) of malononitrile (commercially obtained from Sigma-Aldrich, Milwaukee, WI), 20 drops of piperidine (commercially obtained from Sigma-Aldrich, Milwaukee, WI) were added to a 2-liter, 3-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser. The solution was refluxed for 8 hours, and the flask was cooled to room temperature. The orange crude product was filtered, washed twice with 70 ml of methanol and once with 150 ml of water, and dried in the hood for overnight. This orange crude product was recrystallized from a mixture of 600 ml of acetone and 300 ml of methanol using activated charcoal. The flask was placed at 0 °C for 16 hours. The crystals were filtered and dried in a vacuum oven at 50 °C for 6 hours to obtain 60 g of pure (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile. The melting point of the product was 99-100 °C. A ¹H-NMR spectrum of (4-n-butoxycarbonyl-9-fluorenylidene) malononitrile was obtained in CDCl₃ with a 300 MHz NMR from Bruker Instrument. The peaks (in ppm) were found at δ= 0.74 - 1.16 (t, 3H); δ = 1.38 - 1.72 (m, 2H); δ = 1.70 -1.90 (q, 2H); δ = 4.29 - 4.55 (t, 2H); δ = 7.31 - 7.43 (m, 2H); δ = 7.45 - 7.58 (m, 1H); δ = 7.81 - 7.91 (dd, 1H); δ = 8.15 - 8.25 (dd, 1H); δ = 8.42 - 8.52 (dd, 1H); δ = 8.56 -8.66 (dd, 1H).

Preparation of n-Butyl Fluorenone-4-carboxylate Ester

Fluorenone-4-carboxylic acid (70 g, 0.312 mole, commercially available from Aldrich, Milwaukee, WI), n-butanol (480 g, 6.5 mole, commercially obtained from Fisher Scientific Company Inc., Hanover Park, IL), 1000 ml of toluene and 4 ml of concentrated sulfuric acid were added to a 2-liter round bottom flask equipped with a mechanical stirrer and a reflux condenser with a Dean Stark apparatus. The solution was refluxed for 5 hours with aggressive agitation and refluxing, during which time about 6 g of water were collected in the Dean Stark apparatus. The flask was cooled to room temperature. The solvents were evaporated, and the residue was added to 4-liter of 3% sodium bicarbonate aqueous solution with agitation. The solid was filtered off, washed with water until the pH of the water was neutral, and dried in the hood overnight. The product was n-butyl fluorenone-4-carboxylate ester (70 g, 80% yield). A ¹H-NMR spectrum of n-butyl fluorenone-4-carboxylate ester was obtained in CDCl₃ with a 300 MHz NMR from Bruker Instrument. The peaks (in ppm) were found at δ = 0.87 -1.09 (t, 3H); δ = 1.42 - 1.70 (m, 2H); δ = 1.75 - 1.88 (q, 2H); δ = 4.26 -4.64 (t, 2H); δ = 7.29 -7.45 (m, 2H); δ = 7.46 -7.58 (m, 1H); δ = 7.60 - 7.68 (dd, 1H); δ = 7.75 - 7.82 (dd, 1H); δ = 7.90 -8.00 (dd, 1H); δ = 8.25 - 8.35 (dd, 1H).

Preparation of 4-n-Butoxycarbonyl-9-fluorenone Hydrazone

A 56.0 g quantity of n-butyl fluorenone-4-carboxylate ester (0.2 mole, prepared previously), 200 ml of ethanol, 12.82 g of anhydrous hydrazine (0.4 mole, obtained from Aldrich Chemicals, Milwaukee, WI) were added to a 500 ml 3-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser. The flask was heated at 74 °C for 5 hours. Then, the solution was kept at 0 °C for overnight. A yellow solid was filtered off and washed with 50 ml of ethanol and dried at 50 °C oven vacuum for 8 hours. The yield was 49g (83%). A ¹H-NMR spectrum in CDCl₃ yielded measurements of chemical shifts (ppm) (using 300 MHz H-NMR Bruker instrument): Aliphatic protons - δ = 0.9-1.11 (t, 3H); δ = 1.40-1.63 (m, 2H); δ = 1.71-1.90 (m, 2H); δ = 4.36-4.50 (t, 2H). The NH₂ has two broad singlets at δ = 6.35 - 6.66. The aromatic protons appeared in the range of δ = 7.28 - 8.52.

Preparation of Compound (2)

Carbazole (120 g, 0.72 mole, obtained from Aldrich, Milwaukee, WI), 1,10-dibromodecane (100 g, 0.33 mole, obtained from Aldrich, Milwaukee, WI), benzyltriethyl ammonium chloride (12 g, obtained from Aldrich, Milwaukee, WI) and 400 ml of tetrahydrofuran (THF) were added to a 2-liter 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The flask was stirred at room temperature until all solid entered into solution. A concentrated solution of sodium hydroxide (120 g) in water (120 ml) was added to the solution. The mixture was heated at reflux with strong mechanical stirring for 4 hours, then cooled to room temperature and poured into an excess of water. The solid that precipitated was filtered off, and the THF layer was dried over magnesium sulfate and concentrated to dryness. The combined organic solids were recrystallized from THF/water and dried at 50 °C for 6 hours. The yield was 116.5 g (69%). The product had a melting point of 130 °C.
Dimethylformamide (200 ml, obtained from Aldrich, Milwaukee, WI) was added to 1-liter 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The flask was cooled in ice bath. Phosphorous oxychloride (70 ml, 115 g, 0.75 mole, obtained from Aldrich, Milwaukee, WI) was added gradually. The temperature of the flask was not allowed to rise above 5 °C during the addition of phosphorous oxychloride. 1, 10-bis (9-carbazoyl) decane (100 g, 0.22 mole, prepared in previous step) was introduced, and the resulting mixture was heated on steam bath with stirring for 1.5 hours. A viscous, dark brown liquid was generated from which a yellow solid precipitated upon cooling. The entire mixture was added to water (400 ml). The crude product was filtered off, washed with water (200 ml) and then with ethanol (70 ml). Recrystallization from THF/water afforded 1,10-bis (3-formyl-9-carbazolyl) decane as light brown crystals. The yield was 92.3 g (83%), and the composition had a melting point of 122 °C
1,10-bis (3-formyl-9-carbazolyl) decane (10.0 g, 0.019 mole, prepared in previous step) and 150 ml of tetrahydrofuran (THF) were added to a 500 ml 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The flask was heated with a heating mantle until all solid entered to solution. A solution of the 9-fluorenone-4-n-butylcarboxylate hydrazone (11.23 g, 0.0381 mole, prepared as described above) in 50 ml of tetrahydrofuran was added to the flask followed by the addition of 10 drops of 37% aqueous hydrochloric acid. The flask was refluxed for 5 hours. Activated charcoal was added, and the solution was boiled for about 5 minutes. After boiling, the solution was filtered hot into a beaker that contains 500 ml of ethyl alcohol. The product was isolated and recrystallized from THF/ethyl alcohol with activated charcoal. The product was isolated and dried at 50 °C oven vacuum for 6 hours. The yield was 7.85 g (40%).

Preparation of Compound (3)

A 70 g (0.312 mole) quantity of fluorenone-4-carboxylic acid, 300 g (6.5 mole) of ethyl alcohol (commercially obtained from Aldrich Chemicals, Milwaukee, WI), 1000 ml of toluene and 4 ml of concentrated sulfuric acid were added to a 2-liter round bottom flask equipped with a mechanical stirrer and a reflux condenser with a Dean Stark apparatus. With aggressive agitation and refluxing, the solution was refluxed for 5 hours, during which time about 6 g of water were collected in the Dean Stark apparatus. The flask was cooled to room temperature. The solvents were evaporated and the residue was added, with agitation, to 4-liter of a 3% sodium bicarbonate aqueous solution. The solid was filtered off, washed with water until the pH of the wash-water was neutral, and dried in the hood overnight. The product was ethyl fluorenone-4-carboxylate ester. The yield was 65 g (83%). A ¹H-NMR spectrum of ethyl fluorenone-4-carboxylate ester was obtained in CDCl₃ with a 300 MHz NMR from Bruker Instrument. The peaks for the aliphatic region were found at (ppm) δ= 1.38 -1.53 (t, 3H); δ = 4.40 - 4.59 (q, 2H). The aromatic region has several peaks at δ = 7.30 - 8.33.
A 50.45 g quantity of ethyl fluorenone-4-carboxylate ester (0.2 mole, prepared previously), 200 ml of ethanol, 12.82 g of anhydrous hydrazine (0.4 mole, obtained from Aldrich Chemicals, Milwaukee, WI) were added to a 500 ml 3-neck round bottom flask equipped with a mechanical stirrer and a reflux condenser. The flask was heated at 74 °C for 5 hours. The solution was kept at 0 °C for overnight. A yellow solid was filtered off, washed with 50 ml of ethanol, and dried at 50 °C oven vacuum for 8 hours. The yield of product was 40 g (76%). A ¹H-NMR spectrum in CDCl₃ yielded the following chemical shifts (ppm) (using 300 MHz H-NMR Bruker instrument): Aliphatic protons: δ = 1.38 - 1.53 (t, 3H); δ = 4.40 - 4.59 (q, 2H). The NH₂ has two broad singlets at δ = 6.35 - 6.61. The aromatic protons appeared in the range of δ = 7.28 - 8.52.
1,10-bis (3-formyl-9-carbazolyl)decane (10.0 g, 0.019 mole) and 150 ml of tetrahydrofuran (THF) were added to a 500 ml 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The flask was heated with a heating mantle until all solid entered to solution. A solution of the 9-fluorenone-4-ethylcarboxylate hydrazone (10.15 g, 0.0381 mole, prepared previously) in 50 ml of tetrahydrofuran was added to the flask followed by the addition of 10 drops of 37% aqueous hydrochloric acid. The flask was refluxed for 5 hours. Activated charcoal was added, and the solution was boiled for about 5 minutes and then filtered hot into a beaker that contained 500 ml of ethyl alcohol. The product was isolated and recrystallized from THF/ethyl alcohol with activated charcoal. The product was isolated and dried at 50 °C oven vacuum for 6 hours. The yield was 8.0 g (42%).

Preparation of Compound (4)

A solution of carbazole (22 g, 0.13 mole, obtained from Aldrich, Milwaukee, WI) in dry THF (200 ml) was added over 40 minutes to a suspension of sodium hydride (60% in mineral oil, 5.9 g, 0.15 mole, obtained from Aldrich, Milwaukee, WI) in dry THF (75 ml) under a nitrogen atmosphere. After 30 minutes, a solution of 1, 12-dibromododecane (20 g, 0.06 mole, obtained from Aldrich, Milwaukee, WI) in dry THF (80 ml) was added, and the mixture was refluxed under nitrogen with magnetic stirrer for 3 hours. Once cooled to room temperature, the mixture was diluted with diethyl ether (100 ml), washed with water (2 x 50 ml), dried over magnesium sulfate, and concentrated to give a viscous oil. This oil was triturated with 40-60 °C petroleum ether, and a resulting solid was filtered off and dried in a 50 °C vacuum oven to give 24.8 g (83%) of 1,12-bis(9-carbazolyl)decane. The product had a melting point of 98-99 °C.
Dimethylformamide (30 ml) was stirred and cooled in an ice bath while phosphorus oxychloride (8.3 ml, 13.7 g, 90 mmole) was added gradually. 1, 12-bis (9-carbazolyl) dodecane (14.6 g, 29 mmole, obtained in previous step) was introduced, and the resulting mixture was heated on a steam bath with stirring for 2 hours. Upon cooling, the resulting viscous, dark brown liquid was added to a saturated solution of sodium acetate. The aqueous solution was decanted off. The remaining organic material was dissolved in dichloromethane (250 ml), washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated by evaporation under a vacuum. The crude product was recrystallized from toluene/THF and then dried in a vacuum oven at 60 °C. 1, 12-bis (3-formylcarbazolyl) dodecane was isolated as light brown crystals. The yield was 8.8 g (55%). The product had a melting point of 149 °C.
Compound (4) can be obtained by reacting dialdeyhde (prepared in previous step) with 9-fluorenone-4-n-butylcarboxylate hydrazone (prepared above) under similar conditions used to obtain Compound (2).

Preparation of Compound (5)

A solution of N-(hydroxyethyl)carbazole (10.55 g, obtained from Aldrich, Milwaukee, WI) and triethylamine (10 ml, obtained from Aldrich, Milwaukee, WI) in dichloromethane (100 ml) was cooled to 0 °C. Adipoyl chloride (3.6 ml, obtained from Aldrich, Milwaukee, WI) was added drop wise with stirring. The solution was allowed to warm to room temperature and stirring was continued for an additional 2 hours. After washing with water (2 x 100 ml), the solvent was evaporated to give the crude solid product. Recrystallization from ethyl acetate: petroleum ether (1:2) afforded bis(carbazolyl)ethyl adipoate as a white solid product. The yield was 5.6 g (42%).
A solution of bis(carbazolyl)ethyl adipoate (5.6 g, obtained in previous step) in dimethylformamide (10 ml) was added at 0 °C to Vilsmier reagent formed from phosphorous oxychloride (4 ml) and dimethylformamide (20 ml). The mixture was heated at 80 °C for 2 hours and then poured onto ice and potassium acetate. The crude product was collected by filtration and recrystallized from petroleum ether to give bis (3-formylcarbazolyl)ethyl adipoate (2.6 g, 42%)
Compound (5) can be obtained by reacting the dialdeyhde (prepared in previous step) with 9-fluorenone-4-n-butylcarboxylate hydrazone under similar conditions used to obtain Compound (2).

Preparation of Compound (6)

1,2-bis (2-iodoethoxy)ethane (49.96 g, 135 mmole, obtained from Aldrich, Milwaukee, WI), carbazole (48.54 g, 290 mmole), benzyltriethyl ammonium chloride (4.8 g), sodium hydroxide (50 g) in water (50 ml) and 200 ml of toluene were added to a 250 ml 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The mixture was heated at reflux for 6 hours. The mixture was left stirring at room temperature overnight. The precipitate was collected by filtration and washed with toluene (30 ml) and water (1 liter). The product was dried at 50 °C vacuum oven for 6 hours. The yield was 46.75 g. The product had a melting point of 125-128 °C.
The carbazole dimer (7.03 g, 15.7 mmole, prepared in previous step) was converted to a dialdehyde by reaction with phosphorous oxychloride (4.5 ml, 45 mmole) in dimethylformamide (15 ml) in a manner similar to Compound (2).
Compound (6) can be obtained by reacting dialdeyhde (prepared in the previous step) with 9-fluorenone-4-n-butylcarboxylate hydrazone under similar conditions used to obtain Compound (2).

Example 2 - Preparation of Organophotoreceptors

Comparative Sample A

Comparative Sample A was a single layer organophotoreceptor coated on a 30 mm diameter anodized aluminum drum substrate. The coating solution for the single layer organophotoreceptor was prepared by pre-mixing 2.4 g of 20 weight % (4-n-butoxycarbonyl-9-fluorenylidene)malononitrile in tetrahydrofuran, 6.66 g of 25 weight % MPCT-10 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 7.65 g of 12 weight % polyvinyl butyral resin (BX-1, commercially obtained from Sekisui Chemical Co. Ltd., Japan) in tetrahydrofuran. A 0.74 g quantity of a CGM mill-base containing 19 weight % of titanyl oxyphthalocyanine and a polyvinyl butyral resin (BX-5, commercially obtained from Sekisui Chemical Co. Ltd., Japan) at a weight ratio of 2.3:1 was then added to the above mixture. The Charge Generating Material (CGM) mill-base was obtained by milling 112.7 g of titanyl oxyphthalocyanine (commercially obtained from H.W. Sands Corp., Jupiter, FL) with 49 g of the polyvinyl butyral resin (BX-5) in 651 g of methylethylketone on a horizontal sand mill (model LMC12 DCMS, commercially obtained from Netzsch Incorporated, Exton, PA) with 1-micron zirconium beads using recycle mode for 4 hours. After mixing the solution on a mechanical shaker for about 1 hour, the single layer coating solution was ring coated onto the 30 mm diameter anodized aluminum drum at a rate of about 175 mm/min. The coated drum was dried in an oven at 110 °C for 5-10 minutes. The dry photoconductor film thickness was 12 microns, ± 0.5 microns.

Comparative Sample B

Comparative sample B was prepared similar to sample A except that the ring coating rate was increased to produce a dry film thickness of 15 µ.

Comparative Sample C

Comparative sample C was prepared similar to sample A except that the ring coating rate was increased to produce a dry film thickness of 22 µ.

Sample 1

Sample 1 was a single layer organophotoreceptor coated on a 30 mm diameter anodized aluminum drum substrate. The coating solution for the single layer organophotoreceptor was prepared by pre-mixing 2.4 g of 20 weight % Compound (2) in THF, 6.66 g of 25 weight % MPCT-10 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 7.65 g of 12 weight % polyvinyl butyral resin (BX-1, commercially obtained from Sekisui Chemical Co. Ltd., Japan) in tetrahydrofuran. A 0.74 g quantity of a CGM mill-base containing 19 weight % of titanyl oxyphthalocyanine and a polyvinyl butyral resin (BX-5, commercially obtained from Sekisui Chemical Co. Ltd., Japan) at a weight ratio of 2.3:1 was then added to the above mixture. The CGM mill-base was obtained by milling 112.7 g of titanyl oxyphthalocyanine (commercially obtained from H.W. Sands Corp., Jupiter, FL) with 49 g of the polyvinyl butyral resin (BX-5) in 651 g of methylethylketone on a horizontal sand mill (model LMC12 DCMS, commercially obtained from Netzsch Incorporated, Exton, PA) with 1-micron zirconium beads using recycle mode for 4 hours. After mixing on a mechanical shaker for about 1 hour, the single layer coating solution was ring coated onto the 30 mm diameter anodized aluminum drum at a rate of about 195 mm/min. The coated drum was dried in an oven at 110 °C for 5-10 minutes. The dry photoconductor film thickness was 13 microns ± 0.5 microns.

Sample 2

Sample 2 was prepared similar to Sample 1, except that the ring coating rate was increases to produce a dried film thickness of 18 µ.

Sample 3

Sample 3 was prepared similar to Sample 1, except that Compound (3) was used instead of Compound (2), and the ring coating rate was increased to produce a dry film thickness of 14µ.

Sample 4

Sample 4 was prepared similar to Sample 1, except that Compound (3) was used instead of Compound (2), and the ring coating rate was increased to produce a dry film thickness of 17µ.

Sample 5

Sample 5 was a single layer organophotoreceptor coated on a 30 mm diameter anodized aluminum drum substrate. The coating solution for the single layer organophotoreceptor was prepared by pre-mixing 2.4 g of 20 weight % Compound (2) in THF, 6.66 g of 25 weight % MPCT-38 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 7.65 g of 12 weight % polyvinyl butyral resin (BX-1, commercially obtained from Sekisui Chemical Co. Ltd., Japan) in tetrahydrofuran. A 0.74 g quantity of a CGM mill-base containing 19 weight % of titanyl oxyphthalocyanine and a polyvinyl butyral resin (BX-5, commercially obtained from Sekisui Chemical Co. Ltd., Japan) at a weight ratio of 2.3:1 was then added to the above mixture. The CGM mill-base was obtained by milling 112.7 g of titanyl oxyphthalocyanine (commercially obtained from H.W. Sands Corp., Jupiter, FL) with 49 g of the polyvinyl butyral resin (BX-5) in 651 g of methylethylketone on a horizontal sand mill (model LMC12 DCMS, commercially obtained from Netzsch Incorporated, Exton, PA) with 1-micron zirconium beads using recycle mode for 4 hours. After mixing on a mechanical shaker for about 1 hour, the single layer coating solution was ring coated onto the 30 mm diameter anodized aluminum drum at a rate of about 250 mm/min. The coated drum was dried in an oven at 110 °C for 5-10 minutes. The dry photoconductor film thickness was 16 µ.

Sample 6

Sample 6 was made similar to Sample 5 except that the coating rate was increased to produce a dry film thickness of 23 µ.

Sample 7

Sample 7 was a single layer organophotoreceptor coated on a 30 mm diameter anodized aluminum drum substrate. The coating solution for the single layer organophotoreceptor was prepared by pre-mixing 2.4 g of 20 weight % Compound (2) in THF, 3.33 g of 25 weight % MPCT-10 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 3.33 g of 25 weight % MPCT-38 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 7.65 g of 12 weight % polyvinyl butyral resin (BX-1, commercially obtained from Sekisui Chemical Co. Ltd., Japan) in tetrahydrofuran. A 0.74 g quantity of a CGM mill-base containing 19 weight % of titanyl oxyphthalocyanine and a polyvinyl butyral resin (BX-5, commercially obtained from Sekisui Chemical Co. Ltd., Japan) at a weight ratio of 2.3:1 was then added to the above mixture. The CGM mill-base was obtained by milling 112.7 g of titanyl oxyphthalocyanine (commercially obtained from H.W. Sands Corp., Jupiter, FL) with 49 g of the polyvinyl butyral resin (BX-5) in 651 g of methylethylketone on a horizontal sand mill (model LMC12 DCMS, commercially obtained from Netzsch Incorporated, Exton, PA) with 1-micron zirconium beads using recycle mode for 4 hours. After mixing on a mechanical shaker for about 1 hour, the single layer coating solution was ring coated onto the 30 mm diameter anodized aluminum drum at a rate of about 250 mm/min. The coated drum was dried in an oven at 110 °C for 5-10 minutes. The dry photoconductor film thickness was 16 µ.

Sample 8

Sample 8 was prepared similar to Sample 7 except that the ring coating rate was increased to produce a dry film thickness of 22 µ.

Sample 9

Sample 9 was a single layer organophotoreceptor coated on a 30 mm diameter anodized aluminum drum substrate. The coating solution for the single layer organophotoreceptor was prepared by pre-mixing 1.2 g of 20 weight % Compound (2) in THF, 1.2 g of 20 weight % ET400 (a hydroquinone derivative commercially available from Takasago Chemical Corp., Tokyo Japan), 6.66 g of 25 weight % MPCT-10 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 7.65 g of 12 weight % polyvinyl butyral resin (BX-1, commercially obtained from Sekisui Chemical Co. Ltd., Japan) in tetrahydrofuran. A 0.74 g quantity of a CGM mill-base containing 19 weight % of titanyl oxyphthalocyanine and a polyvinyl butyral resin (BX-5, commercially obtained from Sekisui Chemical Co. Ltd., Japan) at a weight ratio of 2.3:1 was then added to the above mixture. The CGM mill-base was obtained by milling 112.7 g of titanyl oxyphthalocyanine (commercially obtained from H.W. Sands Corp., Jupiter, FL) with 49 g of the polyvinyl butyral resin (BX-5) in 651 g of methylethylketone on a horizontal sand mill (model LMC12 DCMS, commercially obtained from Netzsch Incorporated, Exton, PA) with 1-micron zirconium beads using recycle mode for 4 hours. After mixing on a mechanical shaker for about 1 hour, the single layer coating solution was ring coated onto the 30 mm diameter anodized aluminum drum at a rate of about 250 mm/min. The coated drum was dried in an oven at 110 °C for 5-10 minutes. The dry photoconductor film thickness was 16µ.

Sample 10

Sample 10 was prepared similar to Sample 9 except that the ring coating rate was increased to produce a dry film thickness of 22µ.

Sample 11

Sample 11 was a single layer organophotoreceptor coated on a 30 mm diamter anodized aluminum drum substrate. The coating solution for the single layer organophotoreceptor was prepared by pre-mixing 2.16 g of 20 weight % Compound (2) in THF, 0.24 g of 20 weight % ET400 (a hydroquinone derivative commercially available from Takasago Chemical Corp., Tokyo, Japan), 6.66 g of 25 weight % MPCT-10 (a charge transfer material, commercially obtained from Mitsubishi Paper Mills, Tokyo, Japan) in tetrahydrofuran, 7.65 g of 12 weight % polyvinyl butyral resin (BX-1, commercially obtained from Sekisui Chemical Co. Ltd., Japan) in tetrahydrofuran. A 0.74 g quantity of a CGM mill-base containing 19 weight % of titanyl oxyphthalocyanine and a polyvinyl butyral resin (BX-5, commercially obtained from Sekisui Chemical Co. Ltd., Japan) at a weight ratio of 2.3:1 was then added to the above mixture. The CGM mill-base was obtained by milling 112.7 g of titanyl oxyphthalocyanine (commercially obtained from H.W. Sands Corp., Jupiter, FL) with 49 g of the polyvinyl butyral resin (BX-5) in 651 g of methylethylketone on a horizontal sand mill (model LMC12 DCMS, commercially obtained from Netzsch Incorporated, Exton, PA) with 1-micron zirconium beads using recycle mode for 4 hours. After mixing on a mechanical shaker for about 1 hour, the single layer coating solution was ring coated onto the 30 mm diamter anodized aluminum drum at a rate of about 285 mm/min. The coated rum was dried in an oven at 110 °C for 5-10 minutes. The dry photoconductor film thickness was 18µ.

Sample 12

Sample 12 was prepared similar to Sample 11 except that the ring coating rate was increased to produce a dry film thickness of 23 µ.

Example 3 - Electrostatic Testing And Properties Of Organophotoreceptors

This example provides results of electrostatic testing on the organophotoreceptor samples formed as described in Example 1.

Electrostatic cycling performance of organophotoreceptors described herein with azine compounds can be determined using in-house designed and developed test bed. Electrostatic evaluation on the 30 mm drum test bed is designed to accelerate electrostatic fatigue during extended cycling by increasing the charge-discharge cycling frequency and decreasing the recovery time as compared to drum test beds with longer process speeds. The location of each station in the tester (distance and elapsed time per cycle) is given as follows.

Electrostatic test stations around the 30 mm drum at 12.7 cm /s.

Station	Degrees	Total Distance, cm	Total Time, sec
Erase Bar Center	0°	Initial, 0 cm	Initial, 0 s
Corotron Charger	87.3°	2.29	0.18
Laser Strike	147.7°	3.87	0.305
Probe #1	173.2°	4.53	0.36
Probe #2	245.9°	6.44	0.51
Erase Bar Center	360°	9.425	0.74

The erase bar is an array of laser emitting diodes (LED) with a wavelength of 720 nm. that discharges the surface of the organophotoreceptor. The corotron charger comprises a wire that permits the transfer of a charge to the surface of the organophotoreceptor at fast processing speeds.

From the table, the first electrostatic probe (Trek^™ 344 electrostatic meter) is located 0.055 s after the laser strike station and 0.18 s after the corotron charger. Also, the second probe (Trek 344 electrostatic meter) is located 0.15 s from the first probe and 0.33 s from the corotron charger. All measurements were performed at 20°C and 30% relative humidity.
Electrostatic measurements were obtained as a compilation of several tests. The first three diagnostic tests (prodtest initial, VlogE initial, dark decay initial) are designed to evaluate the electrostatic cycling of a new, fresh sample and the last three, identical diagnostic test (prodtest final, VlogE final, dark decay final) are run after cycling of the sample (longrun). The laser is operated at 780nm, 600dpi, 50 um spot size, 60 nanoseconds / pixel expose time, 1,800 lines per second scan speed, and a 100% duty cycle. The duty cycle is the percent exposure of the pixel clock period, i.e., the laser is on for the full 60 nanoseconds per pixel at a 100% duty cycle.

Electrostatic Test Suite:

1) PRODTEST: Charge acceptance (V_acc) and discharge voltage (V_dis) were established by subjecting the samples to corona charging (erase bar always on) for three complete drum revolutions (laser off); discharged with the laser @ 780nm & 600dpi on the forth revolution (50 um spot size, expose 60 nanoseconds / pixel, run at a scan speed of 1,800 lines per second, and use a 100% duty cycle); completely charged for the next three revolutions (laser off); discharged with only the erase lamp @ 720nm on the eighth revolution (corona and laser off) to obtain residual voltage (V_res); and, finally, completely charged for the last three revolutions (laser off). The contrast voltage (V_con) is the difference between V_acc and V_dis and the functional dark decay (V_dd) is the difference in charge acceptance potential measured by probes #1 and #2.
2) VLOGE: This test measures the photoinduced discharge of the photoconductor to various laser intensity levels by monitoring the discharge voltage of the sample as a function of the laser power (exposure duration of 50 ns) with fixed exposure times and constant initial potentials. This test measures the photoinduced discharge of the photoconductor to various laser intensity levels by monitoring the discharge voltage of the sample as a function of the laser power (exposure duration of 50 ns) with fixed exposure times and constant initial potentials. The functional photosensitivity, S_780nm, and operational power settings can be determined from this diagnostic test.
3) DARK DECAY: This test measures the loss of charge acceptance in the dark with time without laser or erase illumination for 90 seconds and can be used as an indicator of i) the injection of residual holes from the charge generation layer to the charge transport layer, ii) the thermal liberation of trapped charges, and iii) the injection of charge from the surface or aluminum ground plane.
4) LONGRUN: The sample was electrostatically cycled for 500 drum revolutions according to the following sequence per each sample-drum revolution. The sample was charged by the corona, the laser was cycled on and off (80-100° sections) to discharge a portion of the sample and, finally, the erase lamp discharged the whole sample in preparation for the next cycle. The laser was cycled so that the first section of the sample was never exposed, the second section was always exposed, the third section was never exposed, and the final section was always exposed. This pattern was repeated for a total of 500 drum revolutions, and the data was recorded periodically, after every 25th cycle.
5) After the LONGRUN test, the PRODTEST, VLOGE, DARK DECAY diagnostic tests were run again.

The following Table lists the results from the prodtest initial and prodtest final diagnostic runs. The values for the charge acceptance voltage (Vacc, probe #1 average voltage obtained from the third cycle), discharge voltage (Vdis, probe #1 average voltage obtained from the fourth cycle) are reported for the initial and final cycles.

Table 1. Dry Electrostatic Test Results after 500 cycles.

Sample	Prodtest, initial					Prodtest, final
	Vacc	Vdis	Vcon	S780nm	Vres	Vacc	Vdis	Vcon	Vres
Sample 1	926	92	834	222	33	659	77	582	34
Sample 2	1088	97	991	222	34	805	85	720	37
Sample 3	884	124	760	222	44	661	106	555	46
Sample 4	981	140	841	222	50	727	116	611	48
Sample 5	985	129	856	269	36	710	97	613	37
Sample 6	1290	142	1148	222	43	952	125	827	44
Sample 7	1052	111	941	210	38	775	95	680	40
Sample 8	1278	135	1143	236	48	987	122	865	48
Sample 9	1053	69	984	236	28	884	72	812	32
Sample 10	1265	94	1171	236	56	1048	105	943	67
Sample 11	1167	112	1055	222	44	885	100	785	46
Sample 12	1342	133	1209	251	55	1047	129	918	57
Comparative Sample A	905	61	844	210	21	618	58	560	22
Comparative Sample B	967	54	913	236	21	652	55	597	30
Comparative Sample C	1266	62	1204	290	25	864	63	801	34

Note: The data were obtained on a fresh sample at the beginning of cycling and then after 500 cycles. In the above table, the radiation sensitivity (Sensitivity at 780nm in m²/J) of the xerographic process was determined from the information obtained during the VLOGE diagnostic run by calculating the reciprocal of the product of the laser power required to discharge the photoreceptor to ½ of its initial potential, the exposure duration, and 1/spot size.
As understood by those skilled in the art, additional substitution, variation among substituents, and alternative methods of synthesis and use may be practiced within the scope and intent of the present disclosure of the invention. The embodiments above are intended to be illustrative and not limiting. Additional embodiments are within the claims. Although the present invention has been described with reference to particular embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the scope of the invention.
Although a few preferred embodiments have been shown and described, it will be appreciated by those skilled in the art that various changes and modifications might be made without departing from the scope of the invention, as defined in the appended claims.

Claims

An organophotoreceptor comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising:
(a) a charge transport material having the formula
where n is an integer between 2 and 6, inclusive;
R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;

X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups can be optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;

Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and

Z is a fluorenylidene group; and

(b) a charge generating compound.
An organophotoreceptor according to claim 1 wherein Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
An organophotoreceptor according to either of claims 1 and 2 wherein Z is an alkoxycarbonyl-9-fluorenylidene group.
An organophotoreceptor according to claim 3 wherein the alkoxy group in the alkoxycarbonyl-9-fluorenylidene group contains 1 to 20 carbon atoms.
An organophotoreceptor according to claim 1 wherein the charge transport material has a formula selected form the group consisting of the following:
An organophotoreceptor according to any of claims 1 to 5 wherein the photoconductive element further comprises a second charge transport material.
An organophotoreceptor according to claim 6 wherein the second charge transport material comprises a charge transport compound.
An organophotoreceptor according to any of claims 1 to 7 wherein the photoconductive element further comprises a binder.
An electrophotographic imaging apparatus comprising:
(a) a light imaging component; and

(b) an organophotoreceptor oriented to receive light from the light imaging component, the organophotoreceptor comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising
(i) a charge transport material having the formula
where n is an integer between 2 and 6, inclusive;
R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;

X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups can be optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;

Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and

Z is a fluorenylidene group; and

(ii) a charge generating compound.
An electrophotographic imaging apparatus according to claim 9 wherein Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
An electrophotographic imaging apparatus according to either of claims 9 and 10 wherein Z is an alkoxycarbonyl-9-fluorenylidene group.
An electrophotographic imaging apparatus according to claim 11 wherein the alkoxy group in the alkoxycarbonyl-9-fluorenylidene group contains 1 to 20 carbon atoms.
An electrophotographic imaging apparatus according to claim 9, wherein the charge transport material has a formula selected form the group consisting of the following:
An electrophotographic imaging apparatus according to any of claims 9 to 13 wherein the photoconductive element further comprises a second charge transport material.
An electrophotographic imaging apparatus according to claim 14 wherein second charge transport material comprises a charge transport compound.
An electrophotographic imaging apparatus according to any of claims 9 to 15 further comprising a liquid toner dispenser.
An electrophotographic imaging process comprising;
(a) applying an electrical charge to a surface of an organophotoreceptor comprising an electrically conductive substrate and a photoconductive element on the electrically conductive substrate, the photoconductive element comprising
(i) a charge transport material having the formula
where n is an integer between 2 and 6, inclusive;
R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;

X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups can be optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;

Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and

Z is a fluorenylidene group; and

(ii) a charge generating compound.

(b) imagewise exposing the surface of the organophotoreceptor to radiation to dissipate charge in selected areas and thereby form a pattern of charged and uncharged areas on the surface;

(c) contacting the surface with a toner to create a toned image; and

(d) transferring the toned image to substrate.
An electrophotographic imaging process according to claim 17 wherein Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
An electrophotographic imaging process according to either of claims 17 and 18 wherein Z is an alkoxycarbonyl-9-fluorenylidene group.
An electrophotographic imaging process according to claim 19 wherein the alkoxy group in the alkoxycarbonyl-9-fluorenylidene group contains 1 to 20 carbon atoms.
An electrophotographic imaging process according to claim 17 wherein the charge transport material has a formula selected from the group consisting of the following:
An electrophotographic imaging process according to any of claims 17 to 21 wherein the photoconductive element further comprises a second charge transport material.
An electrophotographic imaging process according to claim 22 wherein the second charge transport material comprises a charge transport compound.
An electrophotographic imaging process according to any of claims 17 to 23 wherein the photoconductive element further comprises a binder.
An electrophotographic imaging process according to any of claims 17 to 24 wherein the toner comprises a liquid toner comprising a dispersion of colorant particles in an organic liquid.
A charge transport material having the formula
where n is an integer between 2 and 6, inclusive;
R₁ and R₂ are, independently, H, halogen, carboxyl, hydroxyl, thiol, cyano, nitro, aldehyde group, ketone group, an ether group, an ester group, a carbonyl group, an alkyl group, an alkaryl group, or an aryl group;

X is a linking group having the formula -(CH₂)_m-, branched or linear, where m is an integer between 0 and 20, inclusive, and one or more of the methylene groups can be optionally replaced by O, S, C=O, O=S=O, urethane, urea, an ester group, a NR₃ group, a CHR₄ group, or a CR₅R₆ group where R₃, R₄, R₅, and R₆ are, independently, H, an alkyl group, an alkaryl group, a heterocyclic group, or an aryl group;

Y comprises a bond, C, N, O, S, a branched or linear -(CH₂)_p- group where p is an integer between 0 and 10, an aromatic group, a cycloalkyl group, a heterocyclic group, or a NR₇ group where R₇ is hydrogen atom, an alkyl group, or aryl group, wherein Y has a structure selected to form n bonds with the corresponding X groups; and

Z is a fluorenylidene group.
A charge transport material according to claim 26 wherein Y is a bond and X is a -(CH₂)_m- group where m is an integer between 1 and 20.
A charge transport material according to either of claims 26 and 27 wherein Z is an alkoxycarbonyl-9-fluorenylidene group.
A charge transport material according to claim 28 wherein the alkoxy group in the alkoxycarbonyl-9-fluorenylidene group contains 1 to 20 carbon atoms.
A charge transport material according to claim 26 wherein the charge transport material has a formula selected from the group consisting of the following: